Solid State Ionics最新文献_第3页

PEO/PLA-based high-temperature organic-inorganic composite solid electrolyte for all-solid-state graphite anode Lithium batteries 全固态石墨负极锂电池用PEO/ pla基高温有机无机复合固体电解质

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-24 DOI: 10.1016/j.ssi.2025.117055

Chunzhi Du , Ruitai Liu , Rui Zhou , Hao Wu , Zhiwei Sang , Yunteng Jiang

As the cornerstone of next-generation energy storage technology characterized by high safety and high energy density, the development of all-solid-state lithium batteries relies critically on the advancement of high-performance composite solid electrolytes (CSEs). In this study, LATP inorganic fillers were incorporated into a PEO/PLA/LiTFSI matrix for the first time to fabricate a novel organic–inorganic composite solid electrolyte (CSE) membrane. Using this membrane, an all-solid-state graphite anode battery with an LFP│CSE│C (graphite) configuration was assembled. The CSE film containing 15 wt% LATP demonstrated superior overall performance, exhibiting a room-temperature ionic conductivity of 1.6 × 10⁻⁴ S/cm. This represents an enhancement of approximately five orders of magnitude compared to the pure PEO/PLA/LiTFSI solid polymer electrolyte. At 60 °C, the ionic conductivity reached 9.6 × 10⁻² S/cm, reflecting a 600 % improvement over its room-temperature value. The electrolyte exhibited an electrochemical stability window of 4.8 V and an ion transference number of 0.7. After 100 cycles, the battery demonstrated excellent cycling durability at 0.2C and 60 °C, retaining 96.5 % of its initial capacity—a 10 % improvement in capacity retention—with a Coulombic efficiency of 99.56 %. The PEO/PLA/LiTFSI/LATP composite solid electrolyte (CSE) represents a promising flexible electrolyte system for all-solid-state lithium batteries, offering a viable strategy for advancing the development of current all-solid-state lithium batteries with graphite anodes.

作为具有高安全性和高能量密度特点的下一代储能技术的基石，全固态锂电池的发展关键依赖于高性能复合固体电解质（cse）的进步。在本研究中，首次将LATP无机填料掺入PEO/PLA/LiTFSI基体中，制备了一种新型有机-无机复合固体电解质（CSE）膜。利用该膜，组装了具有LFP│CSE│C（石墨）结构的全固态石墨阳极电池。含有15 wt% LATP的CSE薄膜表现出优异的整体性能，室温离子电导率为1.6 × 10−4 S/cm。与纯PEO/PLA/LiTFSI固体聚合物电解质相比，这代表了大约五个数量级的增强。在60°C时，离子电导率达到9.6 × 10−2 S/cm，比室温提高600%。电解质的电化学稳定窗口为4.8 V，离子转移数为0.7。经过100次循环后，电池在0.2C和60°C下表现出优异的循环耐久性，保留了96.5%的初始容量，容量保留率提高了10%，库仑效率为99.56%。PEO/PLA/LiTFSI/LATP复合固体电解质（CSE）代表了一种有前途的全固态锂电池柔性电解质体系，为推进当前石墨阳极全固态锂电池的发展提供了可行的策略。

{"title":"PEO/PLA-based high-temperature organic-inorganic composite solid electrolyte for all-solid-state graphite anode Lithium batteries","authors":"Chunzhi Du , Ruitai Liu , Rui Zhou , Hao Wu , Zhiwei Sang , Yunteng Jiang","doi":"10.1016/j.ssi.2025.117055","DOIUrl":"10.1016/j.ssi.2025.117055","url":null,"abstract":"<div><div>As the cornerstone of next-generation energy storage technology characterized by high safety and high energy density, the development of all-solid-state lithium batteries relies critically on the advancement of high-performance composite solid electrolytes (CSEs). In this study, LATP inorganic fillers were incorporated into a PEO/PLA/LiTFSI matrix for the first time to fabricate a novel organic–inorganic composite solid electrolyte (CSE) membrane. Using this membrane, an all-solid-state graphite anode battery with an LFP│CSE│C (graphite) configuration was assembled. The CSE film containing 15 wt% LATP demonstrated superior overall performance, exhibiting a room-temperature ionic conductivity of 1.6 × 10−4 S/cm. This represents an enhancement of approximately five orders of magnitude compared to the pure PEO/PLA/LiTFSI solid polymer electrolyte. At 60 °C, the ionic conductivity reached 9.6 × 10−2 S/cm, reflecting a 600 % improvement over its room-temperature value. The electrolyte exhibited an electrochemical stability window of 4.8 V and an ion transference number of 0.7. After 100 cycles, the battery demonstrated excellent cycling durability at 0.2C and 60 °C, retaining 96.5 % of its initial capacity—a 10 % improvement in capacity retention—with a Coulombic efficiency of 99.56 %. The PEO/PLA/LiTFSI/LATP composite solid electrolyte (CSE) represents a promising flexible electrolyte system for all-solid-state lithium batteries, offering a viable strategy for advancing the development of current all-solid-state lithium batteries with graphite anodes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117055"},"PeriodicalIF":3.3,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Organic weak acid pretreatment enables surface-engineered Li-rich cathodes with suppressed voltage decay and enhanced kinetics 有机弱酸预处理使表面工程的富锂阴极具有抑制电压衰减和增强动力学

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-24 DOI: 10.1016/j.ssi.2025.117051

Jinhua Wu , Chao Han , Haijiao Yang , Zhonglei Zhao , Feifei Ling , Hang Zhao

Lithium-rich Mn-based layered oxides (LLOs) are regarded as promising cathodes owing to exceptional energy density and cost-effectiveness. Nevertheless, three primary drawbacks impede their commercialization: insufficient initial Coulombic efficiency (ICE), limited rate capability, and progressive voltage decay. In this study, the effects of pretreatment using an organic weak acid (tannic acid) and an inorganic strong acid (hydrochloric acid) on the structure, morphology, and electrochemical properties of Li_1.2Mn_0.6Ni_0.2O₂(LMNO) are systematically investigated. Acid pretreatment can cause the dissolution of Li₂O and hence increase electrodes ICE. Compared with the pristine LMNO (73.9 %), the ICE values of tannic acid-treated(LTA) and hydrochloric acid-treated (LHC) samples reach 82.6 % and 81.9 %, respectively. Unlike the severe structural damage caused by hydrochloric acid treatment, tannic acid pretreatment generates only nano-vacancy defects and a minor spinel phase on the LMNO surface. These modifications facilitate Li⁺ transport while suppressing capacity and voltage decay. As a result, the LTA sample exhibits superior rate capability (150 mAh g⁻¹ at 5C; 125 mAh g⁻¹ at 8C), good capacity retention (96.3 % after 100 cycles at 1C), and minimal voltage decay (1.24 mV per cycle). This work establishes organic weak acid pretreatment as a scalable strategy to simultaneously address ICE, rate capability, and voltage decay in LLOs.

富锂锰基层状氧化物（LLOs）由于其特殊的能量密度和成本效益而被认为是有前途的阴极。然而，三个主要的缺点阻碍了它们的商业化：初始库仑效率（ICE）不足，速率能力有限，电压逐渐衰减。本研究系统研究了有机弱酸（单宁酸）和无机强酸（盐酸）预处理对Li1.2Mn0.6Ni0.2O2（LMNO）结构、形貌和电化学性能的影响。酸预处理可以引起Li2O的溶解，从而增加电极的ICE。与原始LMNO（73.9%）相比，单宁酸处理（LTA）和盐酸处理（LHC）样品的ICE值分别达到82.6%和81.9%。与盐酸处理造成的严重结构损伤不同，单宁酸预处理只会在LMNO表面产生纳米空位缺陷和少量尖晶石相。这些修饰有利于Li+输运，同时抑制了容量和电压衰减。结果，LTA样品表现出优异的倍率性能（5C时150 mAh g - 1； 8C时125 mAh g - 1），良好的容量保持率（在1C下100次循环后96.3%）和最小的电压衰减（每循环1.24 mV）。这项工作建立了有机弱酸预处理作为一种可扩展的策略，可以同时解决LLOs中的ICE、速率能力和电压衰减问题。

{"title":"Organic weak acid pretreatment enables surface-engineered Li-rich cathodes with suppressed voltage decay and enhanced kinetics","authors":"Jinhua Wu , Chao Han , Haijiao Yang , Zhonglei Zhao , Feifei Ling , Hang Zhao","doi":"10.1016/j.ssi.2025.117051","DOIUrl":"10.1016/j.ssi.2025.117051","url":null,"abstract":"<div><div>Lithium-rich Mn-based layered oxides (LLOs) are regarded as promising cathodes owing to exceptional energy density and cost-effectiveness. Nevertheless, three primary drawbacks impede their commercialization: insufficient initial Coulombic efficiency (ICE), limited rate capability, and progressive voltage decay. In this study, the effects of pretreatment using an organic weak acid (tannic acid) and an inorganic strong acid (hydrochloric acid) on the structure, morphology, and electrochemical properties of Li1.2Mn0.6Ni0.2O2(LMNO) are systematically investigated. Acid pretreatment can cause the dissolution of Li2O and hence increase electrodes ICE. Compared with the pristine LMNO (73.9 %), the ICE values of tannic acid-treated(LTA) and hydrochloric acid-treated (LHC) samples reach 82.6 % and 81.9 %, respectively. Unlike the severe structural damage caused by hydrochloric acid treatment, tannic acid pretreatment generates only nano-vacancy defects and a minor spinel phase on the LMNO surface. These modifications facilitate Li+ transport while suppressing capacity and voltage decay. As a result, the LTA sample exhibits superior rate capability (150 mAh g−1 at 5C; 125 mAh g−1 at 8C), good capacity retention (96.3 % after 100 cycles at 1C), and minimal voltage decay (1.24 mV per cycle). This work establishes organic weak acid pretreatment as a scalable strategy to simultaneously address ICE, rate capability, and voltage decay in LLOs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117051"},"PeriodicalIF":3.3,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A revised bond valence based approach to identify descriptor for correlated migration in superionic conductors 一种改进的基于键价的方法来识别超离子导体中相关迁移描述子

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-24 DOI: 10.1016/j.ssi.2025.117053

Bowei Pu , Zheyi Zou , Bing He , Fan Huang , Zuer Ye , Siqi Shi

Multi-ion correlated migration has become one of the critical features for superionic conductors (SICs). Finding a computable descriptor for correlated migration is a significant step for rational design of SICs. Here, we develop a revised bond valence based approach with the consideration of repulsive interactions between mobile ions to calculate Coulomb repulsion energy of crystal structure (E_c), which can quantify the correlated migration tendency. The SICs in which ion transport is governed by correlated migration are characterized by strong Coulomb repulsion energies, as seen in garnet-type Li₇La₃Zr₂O₁₂ (0.851 eV) and NASICON-type Na_3.15Zr₂Si_2.15P_0.85O₁₂ (0.898 eV). In contrast, the SICs with insignificant correlated migration exhibit much weaker Coulomb repulsion energies, exemplified by Li₃YCl₆ (0.441 eV) and Li₃YBr₆ (0.279 eV). Based on high-throughput calculations of 5226 Li-containing and 9363 Na-containing compounds, a threshold E_c of 0.7 eV is proposed to identify the SICs with significant correlated migration. These findings validate the effectiveness and universality of correlated migration descriptor, providing an efficient approach for the future design of superionic conductors.

多离子相关迁移已成为超离子导体的重要特征之一。为相关迁移寻找一个可计算的描述符是物理系统合理设计的重要一步。在此，我们提出了一种修正的基于键价的方法，考虑了移动离子之间的排斥相互作用来计算晶体结构的库仑排斥能（Ec），它可以量化相关的迁移趋势。离子输运受相关迁移控制的sic具有较强的库仑排斥能，如石榴石型Li7La3Zr2O12 （0.851 eV）和nasicon型Na3.15Zr2Si2.15P0.85O12 （0.898 eV）。相比之下，相关迁移不显著的无机硅的库仑排斥能要弱得多，如Li3YCl6 （0.441 eV）和Li3YBr6 （0.279 eV）。基于5226含锂化合物和9363含na化合物的高通量计算，提出了0.7 eV的阈值Ec来识别具有显著相关迁移的sic。这些发现验证了相关迁移描述符的有效性和通用性，为未来超离子导体的设计提供了一种有效的方法。

{"title":"A revised bond valence based approach to identify descriptor for correlated migration in superionic conductors","authors":"Bowei Pu , Zheyi Zou , Bing He , Fan Huang , Zuer Ye , Siqi Shi","doi":"10.1016/j.ssi.2025.117053","DOIUrl":"10.1016/j.ssi.2025.117053","url":null,"abstract":"<div><div>Multi-ion correlated migration has become one of the critical features for superionic conductors (SICs). Finding a computable descriptor for correlated migration is a significant step for rational design of SICs. Here, we develop a revised bond valence based approach with the consideration of repulsive interactions between mobile ions to calculate Coulomb repulsion energy of crystal structure (Ec), which can quantify the correlated migration tendency. The SICs in which ion transport is governed by correlated migration are characterized by strong Coulomb repulsion energies, as seen in garnet-type Li7La3Zr2O12 (0.851 eV) and NASICON-type Na3.15Zr2Si2.15P0.85O12 (0.898 eV). In contrast, the SICs with insignificant correlated migration exhibit much weaker Coulomb repulsion energies, exemplified by Li3YCl6 (0.441 eV) and Li3YBr6 (0.279 eV). Based on high-throughput calculations of 5226 Li-containing and 9363 Na-containing compounds, a threshold Ec of 0.7 eV is proposed to identify the SICs with significant correlated migration. These findings validate the effectiveness and universality of correlated migration descriptor, providing an efficient approach for the future design of superionic conductors.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117053"},"PeriodicalIF":3.3,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High nickel-rich layered oxide: The intrinsic role of cation substitution and metal-oxide coating in tuning cationic mixing and enhancing electronic conductivity 高富镍层状氧化物：阳离子取代和金属氧化物涂层在调节阳离子混合和提高电子导电性方面的内在作用

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-24 DOI: 10.1016/j.ssi.2025.117066

B. Jeevanantham , D. Vignesh , M.K. Shobana

Lithium-ion batteries (LIBs) with LiNi_xMn_yCo_zO₂ (NMC) cathodes are a promising contender due to their high energy density and cost-effectiveness. The excellent performance metrics of the NMC cathode make it an attractive candidate for electric vehicles. With the high capacity and good cycling of NMC, it also causes cationic disorder, transition metal dissolution, and parasitic side reactions. Doping and coating effectively mitigate these effects, helping to minimize irreversible capacity loss. Metal-oxide coating not only covers the cathode surface but also aids in structural stabilization. X-ray diffraction confirms the layered structure and reduces cation disorder. The I(003)/I(104) ratio increases as the NMC gets modified. XPS measurements validate the oxidation state and the reduction of carbonate content post-modification. The thermoelectric response verifies that NMC-LA exhibits superior electronic conductivity and thermoelectric performance compared to other electrodes. The cathode coating effectively minimizes cation mixing, enhances structural stability, and boosts electronic conductivity.

采用LiNixMnyCozO2 （NMC）阴极的锂离子电池（LIBs）由于其高能量密度和成本效益而成为一种有前途的竞争者。NMC阴极优异的性能指标使其成为电动汽车的有吸引力的候选者。由于NMC的高容量和良好的循环性，它也会引起阳离子紊乱、过渡金属溶解和寄生副反应。掺杂和涂层有效地减轻了这些影响，有助于减少不可逆的容量损失。金属氧化物涂层不仅覆盖了阴极表面，而且有助于结构的稳定。x射线衍射证实了层状结构，减少了阳离子无序性。随着NMC的修正，I(003)/I（104）比值增大。XPS测量证实了氧化状态和改性后碳酸盐含量的降低。热电响应验证了NMC-LA与其他电极相比具有优越的电子导电性和热电性能。阴极涂层有效地减少了阳离子混合，增强了结构稳定性，并提高了电子导电性。

{"title":"High nickel-rich layered oxide: The intrinsic role of cation substitution and metal-oxide coating in tuning cationic mixing and enhancing electronic conductivity","authors":"B. Jeevanantham , D. Vignesh , M.K. Shobana","doi":"10.1016/j.ssi.2025.117066","DOIUrl":"10.1016/j.ssi.2025.117066","url":null,"abstract":"<div><div>Lithium-ion batteries (LIBs) with LiNixMnyCozO2 (NMC) cathodes are a promising contender due to their high energy density and cost-effectiveness. The excellent performance metrics of the NMC cathode make it an attractive candidate for electric vehicles. With the high capacity and good cycling of NMC, it also causes cationic disorder, transition metal dissolution, and parasitic side reactions. Doping and coating effectively mitigate these effects, helping to minimize irreversible capacity loss. Metal-oxide coating not only covers the cathode surface but also aids in structural stabilization. X-ray diffraction confirms the layered structure and reduces cation disorder. The I(003)/I(104) ratio increases as the NMC gets modified. XPS measurements validate the oxidation state and the reduction of carbonate content post-modification. The thermoelectric response verifies that NMC-LA exhibits superior electronic conductivity and thermoelectric performance compared to other electrodes. The cathode coating effectively minimizes cation mixing, enhances structural stability, and boosts electronic conductivity.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117066"},"PeriodicalIF":3.3,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The doping factor approach in solid state ionics 固体离子学中的掺杂因子方法

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-23 DOI: 10.1016/j.ssi.2025.117068

Yoed Tsur, Rawan Halabi

The doping factor approach is a simple, sometimes a “back-of-the-envelope” method, to predict concentrations of native point defects upon doping with aliovalent dopants. The doping factor is defined as the ratio between the concentration of quasi-free electrons in the doped state and their concentration in a reference state, typically at the undoped state. In binary compounds, as long as the Boltzmann statistics hold, the neutrality equation becomes a polynomial equation for the doping factor. Once the doping factor is found, all the concentrations of the native point defects are readily determined. While other computational methods allow us to find those concentrations, it is beneficial for researchers to possess such a simple tool for calculating the resulting new concentrations. Furthermore, this method may be the only one available in cases with small deviations from stoichiometry. The method is explained and demonstrated using a simple case of magnesium oxide, as well as on intrinsic compound oxide semiconductors.

掺杂因子法是一种简单的方法，有时是一种“粗略”的方法，用于预测与共价掺杂剂掺杂后的天然点缺陷浓度。掺杂因子定义为掺杂态准自由电子的浓度与参考态（通常是未掺杂态）准自由电子的浓度之比。在二元化合物中，只要玻尔兹曼统计量成立，中性方程就成为掺杂因子的多项式方程。一旦发现掺杂因素，所有的原生点缺陷的浓度都很容易确定。虽然其他计算方法允许我们找到这些浓度，但对于研究人员来说，拥有这样一个简单的工具来计算产生的新浓度是有益的。此外，这种方法可能是在化学计量偏差很小的情况下唯一可用的方法。本文以氧化镁和本征化合物氧化物半导体为例，对该方法进行了说明和论证。

引用次数: 0

Oxygen reduction reaction kinetics and H/D effects in electrodes in contact with proton-conducting electrolyte BaCe0.9Gd0.1O3-δ 质子导电电解质BaCe0.9Gd0.1O3-δ接触电极的氧还原反应动力学及H/D效应

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-22 DOI: 10.1016/j.ssi.2025.117065

E.P. Antonova , D.A. Osinkin

Solid oxides with proton conductivity have great potential for application in high-temperature electrochemical devices. These devices encompass fuel cells, electrolyzers, hydrogen sensors, and membrane reactors for the production of high-purity hydrogen. In order to ensure the efficient operation of these devices, active electrodes are required. In recent studies, complex oxides with triple proton/electron/oxygen conductivity have been identified as a promising solution. Concurrently, numerous studies have demonstrated that conventional mixed oxygen-ionic/electronic conductors (MIECs) with high electronic conductivity exhibit high efficiency in terms of their use as electrodes with proton-conducting electrolyte. In this study, we investigated the electrochemical behavior of the most popular electrode materials La_0.6Sr_0.4Fe_0.8Co_0.2O_3-δ, La₂NiO_4+δ and La_0.75Sr_0.2MnO_3±δ in contact with BaCe_0.9Gd_0.1O_3-δ electrolyte in terms of oxygen reduction kinetics. A feature of this study was the use of regular and heavy water (D₂O) for the humidification of the air when conducting impedance studies followed by analysis of impedance spectra by the method of distribution of relaxation times (DRT) with the subsequent determination of the stage of the oxygen reduction reaction in which the proton and/or water takes part. On the basis of the obtained results, oxygen adsorption, dissociation, and diffusion are proposed to be the rate-determining steps of the oxygen reduction reaction for La_0.6Sr_0.4Fe_0.8Co_0.2O_3-δ and La_0.75Sr_0.2MnO_3±δ electrodes.

具有质子导电性的固体氧化物在高温电化学器件中具有很大的应用潜力。这些装置包括燃料电池、电解槽、氢传感器和用于生产高纯度氢的膜反应器。为了保证这些器件的高效运行，需要有源电极。在最近的研究中，具有三重质子/电子/氧电导率的复合氧化物被认为是一种很有前途的解决方案。同时，大量研究表明，具有高电子导电性的传统混合氧离子/电子导体（MIECs）作为质子导电电解质的电极具有很高的效率。在本研究中，我们从氧还原动力学的角度研究了最常用的电极材料La0.6Sr0.4Fe0.8Co0.2O3-δ、La2NiO4+δ和La0.75Sr0.2MnO3±δ与BaCe0.9Gd0.1O3-δ电解质接触时的电化学行为。本研究的一个特点是在进行阻抗研究时使用常规水和重水（D2O）对空气进行加湿，然后通过松弛时间分布（DRT）方法分析阻抗谱，随后确定质子和/或水参与的氧还原反应的阶段。在此基础上，提出了la0.6 sr0.4 fe0.8 co0.3 2o3 -δ和La0.75Sr0.2MnO3±δ电极氧还原反应的速率决定步骤为氧吸附、解离和扩散。

{"title":"Oxygen reduction reaction kinetics and H/D effects in electrodes in contact with proton-conducting electrolyte BaCe0.9Gd0.1O3-δ","authors":"E.P. Antonova , D.A. Osinkin","doi":"10.1016/j.ssi.2025.117065","DOIUrl":"10.1016/j.ssi.2025.117065","url":null,"abstract":"<div><div>Solid oxides with proton conductivity have great potential for application in high-temperature electrochemical devices. These devices encompass fuel cells, electrolyzers, hydrogen sensors, and membrane reactors for the production of high-purity hydrogen. In order to ensure the efficient operation of these devices, active electrodes are required. In recent studies, complex oxides with triple proton/electron/oxygen conductivity have been identified as a promising solution. Concurrently, numerous studies have demonstrated that conventional mixed oxygen-ionic/electronic conductors (MIECs) with high electronic conductivity exhibit high efficiency in terms of their use as electrodes with proton-conducting electrolyte. In this study, we investigated the electrochemical behavior of the most popular electrode materials La0.6Sr0.4Fe0.8Co0.2O3-δ, La2NiO4+δ and La0.75Sr0.2MnO3±δ in contact with BaCe0.9Gd0.1O3-δ electrolyte in terms of oxygen reduction kinetics. A feature of this study was the use of regular and heavy water (D2O) for the humidification of the air when conducting impedance studies followed by analysis of impedance spectra by the method of distribution of relaxation times (DRT) with the subsequent determination of the stage of the oxygen reduction reaction in which the proton and/or water takes part. On the basis of the obtained results, oxygen adsorption, dissociation, and diffusion are proposed to be the rate-determining steps of the oxygen reduction reaction for La0.6Sr0.4Fe0.8Co0.2O3-δ and La0.75Sr0.2MnO3±δ electrodes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117065"},"PeriodicalIF":3.3,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dielectric and conductivity studies of Tb-doped zinc orthotitanate nanomaterials for next-generation electronics and energy storage 新一代电子和储能用掺杂tb的正钛酸锌纳米材料的介电和电导率研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-21 DOI: 10.1016/j.ssi.2025.117048

K.M. Girish , R. Lavanya , M.V. Hemantha Reddy , G.R. Rajath , B.N. Deepak Kumar , S.C. Prashantha

Zn₂TiO₄ nanomaterials doped with Terbium were synthesized via a combustion route using oxalyl dihydrazide (ODH) as fuel. The crystalline nature and morphology were confirmed by Powder X-ray diffraction (PXRD), and Scanning Electron Microscopy (SEM) techniques. Optical studies and the nature of liberated organics were conducted through Diffuse Reflectance Spectroscopy (DRS), and Fourier Transform Infrared (FTIR)spectroscopy techniques. Conductivity and Dielectric studies were carried out for the prepared materials and optimized. Dielectric spectra revealed distinct relaxation behaviors at high and low frequencies. Highest dielectric constant was noticed for the 5 mol% Tb-doped Zn₂TiO₄ compared to other compositions. Dielectric plots exhibit a clear merging beyond a certain frequency, and their behavior changes significantly at higher frequencies which can be attributed to the release of space charge and the consequent reduction in the material's barrier properties. The frequency dependence of AC conductivity Tb³⁺ (1–7 mol%): Zn₂TiO₄ nanoparticles follows Jonscher's power law. All the results suggest that the Tb³⁺-doped Zn₂TiO₄ material is potentially suitable for electronics and energy storage applications.

以草酰二肼（ODH）为燃料，通过燃烧途径合成了掺铽纳米Zn2TiO4。通过粉末x射线衍射（PXRD）和扫描电子显微镜（SEM）技术对晶体性质和形貌进行了表征。通过漫反射光谱（DRS）和傅里叶变换红外（FTIR）光谱技术进行光学研究和释放有机物的性质。对制备的材料进行了电导率和介电性能的研究并进行了优化。介质谱在高、低频表现出明显的弛豫行为。与其他组合物相比，5mol % tb掺杂Zn₂TiO₄的介电常数最高。介电图在超过一定频率时表现出明显的合并，其行为在较高频率时发生显著变化，这可归因于空间电荷的释放和随之而来的材料势垒特性的降低。Tb3+ (1 - 7mol %): Zn2TiO4纳米粒子的交流电导率与频率的关系遵循Jonscher幂定律。这些结果表明，Tb3+掺杂的Zn2TiO4材料具有潜在的电子和储能应用潜力。

{"title":"Dielectric and conductivity studies of Tb-doped zinc orthotitanate nanomaterials for next-generation electronics and energy storage","authors":"K.M. Girish , R. Lavanya , M.V. Hemantha Reddy , G.R. Rajath , B.N. Deepak Kumar , S.C. Prashantha","doi":"10.1016/j.ssi.2025.117048","DOIUrl":"10.1016/j.ssi.2025.117048","url":null,"abstract":"<div><div>Zn2TiO4 nanomaterials doped with Terbium were synthesized via a combustion route using oxalyl dihydrazide (ODH) as fuel. The crystalline nature and morphology were confirmed by Powder X-ray diffraction (PXRD), and Scanning Electron Microscopy (SEM) techniques. Optical studies and the nature of liberated organics were conducted through Diffuse Reflectance Spectroscopy (DRS), and Fourier Transform Infrared (FTIR)spectroscopy techniques. Conductivity and Dielectric studies were carried out for the prepared materials and optimized. Dielectric spectra revealed distinct relaxation behaviors at high and low frequencies. Highest dielectric constant was noticed for the 5 mol% Tb-doped Zn₂TiO₄ compared to other compositions. Dielectric plots exhibit a clear merging beyond a certain frequency, and their behavior changes significantly at higher frequencies which can be attributed to the release of space charge and the consequent reduction in the material's barrier properties. The frequency dependence of AC conductivity Tb3+ (1–7 mol%): Zn2TiO4 nanoparticles follows Jonscher's power law. All the results suggest that the Tb3+-doped Zn2TiO4 material is potentially suitable for electronics and energy storage applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117048"},"PeriodicalIF":3.3,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrogen conductivity and anisotropy of ionic conductivity of LiB3O5 crystals LiB3O5晶体的氢电导率和离子电导率的各向异性

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-21 DOI: 10.1016/j.ssi.2025.117046

Mikhail N. Palatnikov, Vladimir A. Sandler, Nikolay V. Sidorov, Olga V. Palatnikova

The defect structure of LBO crystals of different orientations has been studied. Various types of macro-, meso- and micro-defects have been discovered in the crystal structure. Optical microscopy studies revealed the greatest defects in z-oriented LBO crystalline samples. Dendrite fractal structures have spontaneously formed on the surface of LBO samples. Features of the structures indicate internal stresses in the crystalline plates upper layers, and crystal defects. The anisotropy of ionic conductivity of LiB₃O₅ (LBO) crystals containing H⁺ cations as a technological impurity has been studied. A pronounced effect of high-temperature annealing of LBO crystals on the dielectric properties and conductivity features has been found. The obtained results explain some contradictions in the literature data on the phase states, conductivity character and pyroelectric properties of LBO crystals. The contributions of intrinsic (Li⁺) and impurity (H⁺) conductivity have been separated in LBO samples of x, z orientation with small values of intrinsic conductivity, and their temperature dependences have been obtained. The transition temperatures from impurity to intrinsic conductivity with the corresponding increase in the activation enthalpy for x, y, z cuts of LBO crystals have been established. It has been shown that in LBO crystal technology it is desirable to reduce the concentration of doping H⁺ cations.

研究了不同取向LBO晶体的缺陷结构。在晶体结构中发现了各种宏观、中观和微观缺陷。光学显微镜研究揭示了z取向LBO晶体样品中最大的缺陷。LBO样品表面自发形成了枝晶分形结构。这些结构的特征表明了晶片上层的内应力和晶体缺陷。研究了含氢离子为工艺杂质的li3o5 （LBO）晶体离子电导率的各向异性。高温退火对LBO晶体的介电性能和电导率有显著影响。所得结果解释了LBO晶体的相态、电导率和热释电性质等方面的文献数据中存在的矛盾。在x、z两种取向的LBO样品中，本征电导率（Li+）和杂质电导率（H+）的贡献被分离出来，其本征电导率值较小，并得到了它们的温度依赖关系。确定了LBO晶体x、y、z切割从杂质到本征电导率的转变温度和相应的激活焓的增加。研究表明，在LBO晶体技术中，降低掺杂H+阳离子的浓度是可取的。

{"title":"Hydrogen conductivity and anisotropy of ionic conductivity of LiB3O5 crystals","authors":"Mikhail N. Palatnikov, Vladimir A. Sandler, Nikolay V. Sidorov, Olga V. Palatnikova","doi":"10.1016/j.ssi.2025.117046","DOIUrl":"10.1016/j.ssi.2025.117046","url":null,"abstract":"<div><div>The defect structure of LBO crystals of different orientations has been studied. Various types of macro-, meso- and micro-defects have been discovered in the crystal structure. Optical microscopy studies revealed the greatest defects in z-oriented LBO crystalline samples. Dendrite fractal structures have spontaneously formed on the surface of LBO samples. Features of the structures indicate internal stresses in the crystalline plates upper layers, and crystal defects. The anisotropy of ionic conductivity of LiB3O5 (LBO) crystals containing H+ cations as a technological impurity has been studied. A pronounced effect of high-temperature annealing of LBO crystals on the dielectric properties and conductivity features has been found. The obtained results explain some contradictions in the literature data on the phase states, conductivity character and pyroelectric properties of LBO crystals. The contributions of intrinsic (Li+) and impurity (H+) conductivity have been separated in LBO samples of x, z orientation with small values of intrinsic conductivity, and their temperature dependences have been obtained. The transition temperatures from impurity to intrinsic conductivity with the corresponding increase in the activation enthalpy for x, y, z cuts of LBO crystals have been established. It has been shown that in LBO crystal technology it is desirable to reduce the concentration of doping H+ cations.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117046"},"PeriodicalIF":3.3,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Understanding interfacial reactions and electrochemical performance of MoS2 cathodes with laponite-based solid polymer electrolytes 了解二硫化钼阴极与钙钛矿基固体聚合物电解质的界面反应和电化学性能

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-18 DOI: 10.1016/j.ssi.2025.117052

Sneha Mandal , Catherine Tom , Subbiah Alwarappan , Ravi Kumar Pujala , Surendra K. Martha , Vijayamohanan K. Pillai

Solid-state batteries have recently attracted unprecedented interest as potentially safe and stable high-energy storage systems for niche applications. However, modulating the mobility of cations is a challenge, which limits the ionic conductivity and hinders further development of practical devices using these solid electrolytes. The electrode/electrolyte interface is critical in determining the ion transport mechanism, cycle life, and energy storage efficiency in secondary batteries. Here, we report some exciting results on a novel composite polymer electrolyte comprising laponite and nanocellulose, which expands the interlayer gap by ∼2 Å, facilitating a high transference number of 0.84, with a robust electrochemical stability window of 2.7–4.8 V with Na metal. Coupling this electrolyte with few-layer MoS₂ nanosheet cathodes exhibiting expansion along the (001) direction and in-plane compression, we demonstrate charge-discharge with an initial capacity of 17 mAh g⁻¹. FT-IR and Raman analyses reveal hydroxyl groups of cellulose interfere with cathode interface stability, contributing to capacity degradation, while promoting robust anode interface formation. These findings elucidate interfacial reactions impacting performance and suggest that tailored electrode or electrolyte modifications could improve cycling stability in solid-state Na batteries employing laponite-based polymer electrolytes and MoS₂ cathodes.

固态电池作为一种潜在的安全稳定的高能存储系统，最近引起了人们前所未有的兴趣。然而，调节阳离子的迁移率是一个挑战，它限制了离子的电导率，并阻碍了使用这些固体电解质的实用设备的进一步发展。电极/电解质界面是决定二次电池离子传输机制、循环寿命和能量存储效率的关键。在这里，我们报告了一种由拉脱土和纳米纤维素组成的新型复合聚合物电解质的一些令人兴奋的结果，该电解质将层间间隙扩大了~ 2 Å，促进了0.84的高转移数，具有2.7-4.8 V的强大电化学稳定窗口。将这种电解质与具有沿（001）方向膨胀和面内压缩的少层MoS2纳米片阴极耦合，我们展示了初始容量为17 mAh g−1的充放电。FT-IR和拉曼分析显示纤维素的羟基干扰阴极界面的稳定性，导致容量下降，同时促进阳极界面的形成。这些发现阐明了界面反应对性能的影响，并表明定制电极或电解质修饰可以提高采用lapoite基聚合物电解质和MoS2阴极的固态Na电池的循环稳定性。

{"title":"Understanding interfacial reactions and electrochemical performance of MoS2 cathodes with laponite-based solid polymer electrolytes","authors":"Sneha Mandal , Catherine Tom , Subbiah Alwarappan , Ravi Kumar Pujala , Surendra K. Martha , Vijayamohanan K. Pillai","doi":"10.1016/j.ssi.2025.117052","DOIUrl":"10.1016/j.ssi.2025.117052","url":null,"abstract":"<div><div>Solid-state batteries have recently attracted unprecedented interest as potentially safe and stable high-energy storage systems for niche applications. However, modulating the mobility of cations is a challenge, which limits the ionic conductivity and hinders further development of practical devices using these solid electrolytes. The electrode/electrolyte interface is critical in determining the ion transport mechanism, cycle life, and energy storage efficiency in secondary batteries. Here, we report some exciting results on a novel composite polymer electrolyte comprising laponite and nanocellulose, which expands the interlayer gap by ∼2 Å, facilitating a high transference number of 0.84, with a robust electrochemical stability window of 2.7–4.8 V with Na metal. Coupling this electrolyte with few-layer MoS2 nanosheet cathodes exhibiting expansion along the (001) direction and in-plane compression, we demonstrate charge-discharge with an initial capacity of 17 mAh g−1. FT-IR and Raman analyses reveal hydroxyl groups of cellulose interfere with cathode interface stability, contributing to capacity degradation, while promoting robust anode interface formation. These findings elucidate interfacial reactions impacting performance and suggest that tailored electrode or electrolyte modifications could improve cycling stability in solid-state Na batteries employing laponite-based polymer electrolytes and MoS2 cathodes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117052"},"PeriodicalIF":3.3,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effect of LiNbO3 surface dry-coating on the air stability of Ga-doped LLZO solid electrolytes LiNbO3表面干涂对掺ga LLZO固体电解质空气稳定性的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-18 DOI: 10.1016/j.ssi.2025.117056

Hyein Song , Young-Woong Song , Hyochan Lee , Jinsub Lim , Jieun Ryu , Yoojeong Noh , Sung-Won Kang , Seung Heon Lee , Jin Geon Yang , Jaekook Kim , Min-Young Kim

Oxide-based garnet-type Li₇La₃Zr₂O₁₂ (LLZO) solid electrolytes (SEs) have attracted significant attention as promising candidates for next-generation all-solid-state batteries (ASSBs) with high ionic conductivity of 1 × 10⁻³–10⁻⁴ S cm⁻¹. However, LLZO is prone to surface degradation upon exposure to H₂O and CO₂ in the air, leading to the formation of Li₂CO₃ impurities. This not only reduces the ionic conductivity but also increases interfacial resistance with the electrode, ultimately impairing the electrochemical and mechanical performance of the cell. In this study, we investigated and compared the air stability of LiNbO₃-coated Ga-LLZO and the pristine Ga-LLZO. According to the Accelerated Durability Test (ADT), the formation of Li₂CO₃ on the surface of LiNbO₃-coated Ga-LLZO pellets was suppressed compared to the pristine Ga-LLZO. The total ionic conductivity of the pristine Ga-LLZO was 3.90 × 10⁻⁴ S cm⁻¹, while the LiNbO₃-coated Ga-LLZO was 9.17 × 10⁻⁴ S cm⁻¹. Therefore, the ionic conductivity maintenance rates after ADT were 79 % for the LiNbO₃-coated Ga-LLZO, compared to only 23 % for the pristine Ga-LLZO. These results demonstrate that surface coating of Ga-LLZO particles with LiNbO₃ effectively suppresses air degradation reactions and significantly contributes to long-term ionic conductivity maintenance and improved air stability.

氧化基石榴石型Li7La3Zr2O12 （LLZO）固体电解质（SEs）具有1 × 10−3-10−4 S cm−1的高离子电导率，作为下一代全固态电池（assb）的有希望的候选者受到了广泛的关注。然而，LLZO暴露在空气中的H2O和CO2中容易发生表面降解，导致Li2CO3杂质的形成。这不仅降低了离子电导率，还增加了与电极的界面电阻，最终损害了电池的电化学和机械性能。在这项研究中，我们研究并比较了linbo3涂层的Ga-LLZO和原始Ga-LLZO的空气稳定性。通过加速耐久性试验（ADT），与原始Ga-LLZO相比，linbo3涂层的Ga-LLZO球团表面Li2CO3的形成受到抑制。原始Ga-LLZO的总离子电导率为3.90 × 10−4 S cm−1，而涂覆linbo3的Ga-LLZO的总离子电导率为9.17 × 10−4 S cm−1。因此，经过ADT处理后，linbo3涂层的Ga-LLZO的离子电导率维持率为79%，而原始Ga-LLZO的离子电导率仅为23%。这些结果表明，在Ga-LLZO颗粒表面涂覆LiNbO3可以有效抑制空气降解反应，并显著有助于长期维持离子电导率和提高空气稳定性。

{"title":"Effect of LiNbO3 surface dry-coating on the air stability of Ga-doped LLZO solid electrolytes","authors":"Hyein Song , Young-Woong Song , Hyochan Lee , Jinsub Lim , Jieun Ryu , Yoojeong Noh , Sung-Won Kang , Seung Heon Lee , Jin Geon Yang , Jaekook Kim , Min-Young Kim","doi":"10.1016/j.ssi.2025.117056","DOIUrl":"10.1016/j.ssi.2025.117056","url":null,"abstract":"<div><div>Oxide-based garnet-type Li7La3Zr2O12 (LLZO) solid electrolytes (SEs) have attracted significant attention as promising candidates for next-generation all-solid-state batteries (ASSBs) with high ionic conductivity of 1 × 10−3–10−4 S cm−1. However, LLZO is prone to surface degradation upon exposure to H2O and CO2 in the air, leading to the formation of Li2CO3 impurities. This not only reduces the ionic conductivity but also increases interfacial resistance with the electrode, ultimately impairing the electrochemical and mechanical performance of the cell. In this study, we investigated and compared the air stability of LiNbO3-coated Ga-LLZO and the pristine Ga-LLZO. According to the Accelerated Durability Test (ADT), the formation of Li2CO3 on the surface of LiNbO3-coated Ga-LLZO pellets was suppressed compared to the pristine Ga-LLZO. The total ionic conductivity of the pristine Ga-LLZO was 3.90 × 10−4 S cm−1, while the LiNbO3-coated Ga-LLZO was 9.17 × 10−4 S cm−1. Therefore, the ionic conductivity maintenance rates after ADT were 79 % for the LiNbO3-coated Ga-LLZO, compared to only 23 % for the pristine Ga-LLZO. These results demonstrate that surface coating of Ga-LLZO particles with LiNbO3 effectively suppresses air degradation reactions and significantly contributes to long-term ionic conductivity maintenance and improved air stability.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117056"},"PeriodicalIF":3.3,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322995","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0